Me3SiC≡CC(SiMe3)=CH2 | 17963-27-8

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: Me3SiC≡CC(SiMe3)=CH2
• 英文别名: 1-Trimethylsilyl-3-tert-butyl-buten-(3)-in-(1)；(4,4-Dimethyl-3-methylidenepent-1-ynyl)-trimethylsilane
• CAS: 17963-27-8
• 化学式: C₁₁H₂₀Si
• 分子量: 180.365
• InChiKey: LGNRIACDVFVDPL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.47
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  三叔丁基硅烷 、 Me3SiC≡CC(SiMe3)=CH2 在 K[LLa(N(SiMe3)2)2]; L = ArNC(Me)C(Me)NAr, Ar = 2,6-iPr₂C₆H₃ 作用下， 以 甲苯 为溶剂， 反应 8.0h， 以91%的产率得到
  参考文献：
  名称：

  稀土催化的支链 1,3-烯炔选择性 1,4-氢化硅烷化产生四取代甲硅烷基丙二烯

  摘要：

  艾伦烯是有机合成和药物化学中的多功能合成子，因为它们具有多种反应性。1,3-烯炔的催化 1,4-氢化硅烷化可能是合成甲硅烷基丙二烯的直接策略。然而，由于选择性差和底物范围非常有限，过渡金属催化的反应并未成功。我们在此报告了支链 1,3-烯炔的高效和选择性 1,4-氢化硅烷化，由烯-二氨基稀土催化剂使用烷基和芳基氢硅烷实现，导致独家形成四取代的甲硅烷基丙二烯。进行了氘化反应、动力学研究和 DFT 计算以研究可能的机制，揭示了高路易斯酸度、大离子半径和稀土催化剂的结构的关键作用。

  DOI：

  10.1021/jacs.1c04689
• 作为产物：
  描述：

  三甲基氯硅烷 、 2,2-二甲基-3-亚甲基-4-戊炔 生成 Me3SiC≡CC(SiMe3)=CH2
  参考文献：
  名称：

  Stadnichuk,M.D., Journal of general chemistry of the USSR, 1963, vol. 33, p. 1386 - 1389

  摘要：

  DOI：

文献信息

• Displacement of ethene from the decamethyltitanocene-ethene complex with internal alkynes, substituent-dependent alkyne-to-allene rearrangement, and the electronic transition relevant to the back-bonding interaction
  作者：Jiří Pinkas、Róbert Gyepes、Ivana Císařová、Jiří Kubišta、Michal Horáček、Karel Mach

  DOI：10.1039/c5dt00351b

  日期：——

  8 from 1 was inefficient because the equilibrium constant for the reaction [1] + [Me3SiCCSiMe3] ⇌ [8] + [C2H4] approached 1. Compound 9 (R1, R2: Me), not obtainable from 1, together with compounds 3–6 and 10 (R1, R2: Et) were also prepared by alkyne exchange with 8, however this reaction did not take place in attempts to obtain 7. Compounds 1 and 3–9 display the longest-wavelength electronic absorption

  作为二茂钛-乙烯复合物钛[Ti（II）（η 2 -C 2 H ^ 4）（η 5 -C 5我5）2 ]（1）用简单的内炔[R 1 c ^ CR 2给出络合物钛[Ti（II）（ η 2 -R 1 ç CR 2）（η 5 -C 5我5）2 ] R 1，R 2：PH中，Ph（3）中，Ph中，Me（4）中，Me，森达3（5），Ph，SiMe 3（6），t- Bu，SiMe 3（7）和SiMe 3，SiMe 3（8）。与此相反，其中R炔1 =我和R 2 =吨-Bu或I-PR得到丙二烯络合物钛[Ti（II）（η 2 -CH 2 Ç CHR 2）（η 5 -C 5我5）2 ]（11）和（12），而对于R 2 = Et炔烃配合物的混合物（获得13A）和次要的烯丙基（13）。的晶体结构4，6，7和11已被确定; 后一种结构证明了丙二烯末端双键的反向键相互作用。仅从1合成8效率低下，因为反应[ 1 ] + [Me
• Oligomerization and Cross-Oligomerization of Terminal Alkynes Catalyzed by Organoactinide Complexes
  作者：Ariel Haskel、Thomas Straub、Aswini K. Dash、Moris S. Eisen

  DOI：10.1021/ja9836390

  日期：1999.4.1

  Various organoactinides of the type Cp*(2)An(C=CR)(2) (Cp* = C(5)Me(5); An = Th, U) have been synthesized from the corresponding Cp*(2)AnMe(2) complexes by addition of an equimolar amount or an excess of the corresponding terminal alkyne. Attempts to trap the mono(acetylide) complexes Cp*(2)An(C=CR)(Me) were successful for only the transient species Cp*(2)U(C=C(i-Pr))(Me). The bis(acetylide) complexes are active catalysts for the linear oligomerization of terminal alkynes HC=CR. The regioselectivity and the extent of oligomerization depend strongly on the alkyne substituent R, whereas the catalytic reactivities are similar for both organoactinides. Reaction with tert-butylacetylene regioselectively yields the 2,4-disubstituted 1-butene-3-yne dimer, whereas (trimethylsilyl)acetylene is regioselectively trimerized to (E,E)-1,4,6-tris(trimethylsilyl)-1,3-hexadiene-5-yne, with small amounts (3-5%) of the corresponding 2,4-disubstituted 1-butene-3-yne dimer. Oligomerization with less bulky alkyl- and aryl-substituted alkynes produces a mixture of oligomers. Cross-oligomerizations reactions induce the formation of specific cross dimers and trimers. Mechanistic studies on the selective trimerization of HC=CSiMe(3) show that the first step in the catalytic cycle is the C=C bond insertion of the terminal alkyne into the actinide-acetylide bond. The kinetic rate law is first order in organoactinide and in alkyne, with Delta H(double dagger) = 11.1(3) kcal mol(-1) and Delta S(double dagger) = - 45.2(6) eu. The turnover-limiting step is the release of the organic oligomer from the alkenyl-actinide complex. The latter key organometallic intermediate has been characterized by spectroscopic and poisoning studies. A plausible mechanistic scenario is proposed for the oligomerization of terminal alkynes.